JP2006026487A - Method of improving activity of catalyst and performance of semiconductor and method of manufacturing catalyst having improved activity, semiconductor having improved performance and wet solar cell - Google Patents
Method of improving activity of catalyst and performance of semiconductor and method of manufacturing catalyst having improved activity, semiconductor having improved performance and wet solar cell Download PDFInfo
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- JP2006026487A JP2006026487A JP2004206701A JP2004206701A JP2006026487A JP 2006026487 A JP2006026487 A JP 2006026487A JP 2004206701 A JP2004206701 A JP 2004206701A JP 2004206701 A JP2004206701 A JP 2004206701A JP 2006026487 A JP2006026487 A JP 2006026487A
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- 238000000034 method Methods 0.000 title claims abstract description 97
- 239000004065 semiconductor Substances 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 230000000694 effects Effects 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011941 photocatalyst Substances 0.000 claims abstract description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000006872 improvement Effects 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000013081 microcrystal Substances 0.000 claims description 4
- 238000005259 measurement Methods 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
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- 238000010248 power generation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005464 sample preparation method Methods 0.000 description 2
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- 238000009283 thermal hydrolysis Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
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- 238000004332 deodorization Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/545—Microcrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/546—Polycrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
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- Catalysts (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、光触媒を含む触媒の活性向上方法及びシリコン太陽電池のような半導体の性能向上方法、及び、活性が向上した触媒又は性能が向上した半導体の製造方法並びに湿式太陽電池の製造方法に関する。より具体的には、本発明は、触媒、光触媒又は半導体を極低温で冷却することによる活性または性能の向上方法、及び、活性または性能が向上した触媒、光触媒又は半導体の製造方法並びに湿式太陽電池の製造方法に関する。 The present invention relates to a method for improving the activity of a catalyst including a photocatalyst, a method for improving the performance of a semiconductor such as a silicon solar cell, a method for producing a catalyst having improved activity or a semiconductor having improved performance, and a method for producing a wet solar cell. More specifically, the present invention relates to a method for improving activity or performance by cooling a catalyst, photocatalyst or semiconductor at an extremely low temperature, a method for producing a catalyst, photocatalyst or semiconductor having improved activity or performance, and a wet solar cell. It relates to the manufacturing method.
酸化チタンや酸化亜鉛などの酸化物に紫外線を照射して、これらの素材の光触媒作用を発揮させ、その光触媒作用を脱臭や殺菌等に利用することが広く実施されている。これらの素材の光触媒作用を高めるために、これらの酸化物に貴金属を担持させることも知られている。例えば、特許文献１（特開平２−９０９２４号公報）には酸化チタンに金を添着させてアルデヒド類の悪臭を効果的に脱臭することが開示されている。
また、特許文献２（特開平４−２２４３８号公報）には金属のコロイド溶液に半導体酸化物微粒子を混合して半導体酸化物微粒子上に金属を担持させることが開示されている。更に、用いる半導体酸化物の種類、貴金属の種類、貴金属の濃度、担持方法、被分解ガス等によって光触媒特性が大きく変わることも知られており、光触媒活性を向上させるために種々の試みがなされている。また、近時では可視光活性を保有する光触媒も公知であり、たとえば特許文献３（特開２００２−２５５５５４号公報）などがある。可視光応答型光触媒には酸化チタン系のみならず、他の酸化物を主成分としたものがあり、結晶形としてペロブスカイト型やオキシナイトライド型、その他がある。これら可視光応答型光触媒に関しても貴金属を担置し、性能向上を図ることも公知である。
It has been widely practiced to irradiate oxides such as titanium oxide and zinc oxide with ultraviolet rays to exert the photocatalytic action of these materials and to use the photocatalytic action for deodorization or sterilization. In order to enhance the photocatalytic action of these materials, it is also known to support a noble metal on these oxides. For example, Patent Document 1 (Japanese Patent Laid-Open No. 2-90924) discloses that odors of aldehydes are effectively deodorized by attaching gold to titanium oxide.
Patent Document 2 (Japanese Patent Laid-Open No. Hei 4-224438) discloses that semiconductor oxide fine particles are mixed in a metal colloid solution to support the metal on the semiconductor oxide fine particles. Furthermore, it is known that the photocatalytic properties vary greatly depending on the type of semiconductor oxide used, the type of noble metal, the concentration of the noble metal, the loading method, the gas to be decomposed, etc., and various attempts have been made to improve the photocatalytic activity. Yes. Recently, a photocatalyst having visible light activity is also known, for example, Patent Document 3 (Japanese Patent Laid-Open No. 2002-255554). Visible light responsive photocatalysts include not only titanium oxide-based but also other oxides as main components, and crystal forms include perovskite type, oxynitride type, and others. It is also well known that these visible light responsive photocatalysts carry noble metals to improve performance.
このように、光触媒活性を向上させるために種々の試みがなされているが、貴金属は高価な素材であり、貴金属を使用しないで光触媒活性を向上する方法が求められている。 As described above, various attempts have been made to improve photocatalytic activity. However, noble metals are expensive materials, and a method for improving photocatalytic activity without using noble metals is required.
また、光触媒以外の通常の触媒（熱触媒）についても、従来から種々の活性向上方法が考案されているが、新たな活性向上方法に対するニーズも依然として高い。 Moreover, various conventional methods for improving the activity of conventional catalysts (thermal catalysts) other than the photocatalyst have been devised, but the need for a new activity improving method is still high.
さらに、シリコン太陽電池のような半導体は、光の電気へのエネルギー変換効率のような性能の向上が常に求められ、近年、シリコン太陽電池は一般家庭でも実用化が進められていることから、より一層の性能の向上が求められている。
また、いわゆる色素増感型の太陽電池としてグレッチェルセルの名で知られる酸化物半導体である酸化チタンに色素を複合した湿式の太陽電池についても、次世代の太陽電池として発電効率の向上が期待されている。
In addition, wet solar cells that combine dyes with titanium oxide, which is an oxide semiconductor known as the Gretchel cell as a so-called dye-sensitized solar cell, are expected to improve power generation efficiency as next-generation solar cells. Has been.
そこで、本発明の目的は、従来に無い新規な光触媒を含む触媒の活性向上方法及び活性の向上した光触媒を含む触媒の製造方法を提供することにある。
さらに本発明の別の目的は、従来に無い新規な半導体の性能向上方法及び性能の向上した化合物半導体を含む各種半導体及び酸化物半導体と色素を利用した湿式太陽電池の高性能の製造方法を提供することにある。
Accordingly, an object of the present invention is to provide a method for improving the activity of a catalyst containing a novel photocatalyst that has not been heretofore and a method for producing a catalyst containing a photocatalyst with improved activity.
Furthermore, another object of the present invention is to provide a novel method for improving the performance of a new semiconductor and a method for producing a high-performance wet solar cell using various semiconductors, including oxide semiconductors and dyes, including compound semiconductors with improved performance. There is to do.
本発明者は、鋭意検討の結果、酸化チタンを含む光触媒や太陽電池のような半導体を液体窒素温度等の極低温で冷却することにより、冷却処理前の光触媒の活性を上回る性能を発揮する光触媒体や変換効率の高い太陽電池が得られ、冷却条件により、光触媒活性や太陽電池、湿式太陽電池の性能の向上率が異なることを見出して本発明を完成した。
また、本発明は冷却処理後、常温ないし室温に戻し、触媒及び半導体を高性能化することを特徴とした方法でもあり、冷却しながら、または冷却中に半導体を使用する公知の方法とはまったく異なる性能向上方法、ないしは製造方法である。
As a result of intensive studies, the inventor has cooled the semiconductor such as a photocatalyst containing titanium oxide or a solar cell at an extremely low temperature such as a liquid nitrogen temperature, and thereby exhibits a performance exceeding the activity of the photocatalyst before the cooling treatment. The present invention was completed by finding that the solar cell with high body and conversion efficiency was obtained, and that the improvement rate of the photocatalytic activity and the performance of the solar cell and the wet solar cell differed depending on the cooling conditions.
Further, the present invention is also a method characterized in that after cooling treatment, the temperature is returned to room temperature to room temperature to improve the performance of the catalyst and the semiconductor, which is completely different from a known method using a semiconductor while cooling or during cooling. Different performance improvement methods or manufacturing methods.
本発明は以下の通りである。
請求項１の発明は、触媒の活性を向上させる方法であって、触媒を−３０℃以下に冷却し、冷却後昇温することを特徴とする方法である。
請求項２の発明は、活性の向上した触媒の製造方法であって、触媒を−３０℃以下に冷却し、冷却後昇温することを特徴とする方法である。
請求項３の発明は、触媒が酸化物を含む請求項１または２に記載の方法である。
請求項４の発明は、触媒が光触媒である請求項１〜３のいずれか１項に記載の方法である。
請求項５の発明は、光触媒が酸化物半導体である請求項４に記載の方法である。
請求項６の発明は、酸化物半導体が酸化チタンである請求項５に記載の方法である。
請求項７の発明は、半導体の性能を向上させる方法であって、半導体を−３０℃以下に冷却し、冷却後昇温することを特徴とする方法である。
請求項８の発明は、性能の向上した半導体の製造方法であって、半導体を−３０℃以下に冷却し、冷却後昇温することを特徴とする方法である。
請求項９の発明は、半導体がシリコン太陽電池または化合物半導体である請求項８に記載の方法である。
請求項１０の発明は、シリコン太陽電池が単結晶、微結晶、多結晶またはアモルファス型である請求項９に記載の方法である。
請求項１１の発明は、化合物半導体がLEDである請求項９の方法である。
請求項１２の発明は、冷却温度が−５０℃以下である請求項１〜１１のいずれか１項に記載の方法である。
請求項１３の発明は、冷却温度が−８０℃以下である請求項１〜１１のいずれか１項に記載の方法である。
請求項１４の発明は、冷却温度が液体窒素の温度（−１９６℃）である請求項１〜１１のいずれか１項に記載の方法である。
請求項１５の発明は、冷却時間が５分以上である請求項１〜１４のいずれか１項に記載の方法である。
請求項１６の発明は、冷却時間が３０分〜２４時間の範囲である請求項１５に記載の方法である。
請求項１７の発明は、最も低い冷却温度に達するまでの時間が５分以下である請求項 １〜１６のいずれか１項に記載の方法である。
請求項１８の発明は、最も低い冷却温度に達するまでの時間が５分以上である請求項 １〜１６のいずれか１項に記載の方法である。
請求項１９の発明は、最も低い冷却温度に達するまでの時間が１時間以上である請求項 １〜１６のいずれか１項に記載の方法である。
請求項２０の発明は、昇温に要する時間が５分以下である請求項 １〜１６のいずれか１項に記載の方法である。
請求項２１の発明は、昇温に要する時間が５分以上である請求項 １〜１６のいずれか１項に記載の方法である。
請求項２２の発明は、昇温に要する時間が１時間以上である請求項 １〜１６のいずれか１項に記載の方法である。
請求項２３の発明は、触媒、半導体を液体窒素に直接接触させ、冷却する請求項 １〜２２のいずれか１項に記載の方法である。
請求項２４の発明は、冷却後、常温に放置して触媒又は半導体の温度を常温に戻す請求項１〜２３のいずれか１項に記載の方法である。
請求項２５の発明は、請求項１〜８、１２〜２４のいずれかの方法を用いた湿式電池の性能向上方法および製造方法である。
The present invention is as follows.
The invention of claim 1 is a method for improving the activity of the catalyst, wherein the catalyst is cooled to -30 ° C. or lower, and the temperature is raised after cooling.
The invention of claim 2 is a method for producing a catalyst with improved activity, wherein the catalyst is cooled to -30 ° C. or lower, and the temperature is raised after cooling.
The invention according to claim 3 is the method according to claim 1 or 2, wherein the catalyst contains an oxide.
The invention according to claim 4 is the method according to any one of claims 1 to 3, wherein the catalyst is a photocatalyst.
The invention according to claim 5 is the method according to claim 4, wherein the photocatalyst is an oxide semiconductor.
The invention according to claim 6 is the method according to claim 5, wherein the oxide semiconductor is titanium oxide.
The invention of claim 7 is a method for improving the performance of a semiconductor, wherein the semiconductor is cooled to −30 ° C. or lower and the temperature is raised after cooling.
The invention of claim 8 is a method for producing a semiconductor with improved performance, wherein the semiconductor is cooled to -30 ° C. or lower, and the temperature is raised after cooling.
The invention according to claim 9 is the method according to claim 8, wherein the semiconductor is a silicon solar cell or a compound semiconductor.
The invention according to claim 10 is the method according to claim 9, wherein the silicon solar cell is a single crystal, a microcrystal, a polycrystal or an amorphous type.
The invention of claim 11 is the method of claim 9, wherein the compound semiconductor is an LED.
Invention of Claim 12 is a method of any one of Claims 1-11 whose cooling temperature is -50 degrees C or less.
Invention of Claim 13 is a method of any one of Claims 1-11 whose cooling temperature is -80 degrees C or less.
The invention according to claim 14 is the method according to any one of claims 1 to 11, wherein the cooling temperature is the temperature of liquid nitrogen (−196 ° C.).
Invention of Claim 15 is a method of any one of Claims 1-14 whose cooling time is 5 minutes or more.
The invention according to claim 16 is the method according to claim 15, wherein the cooling time is in the range of 30 minutes to 24 hours.
The invention according to claim 17 is the method according to any one of claims 1 to 16, wherein the time to reach the lowest cooling temperature is 5 minutes or less.
The invention according to claim 18 is the method according to any one of claims 1 to 16, wherein the time to reach the lowest cooling temperature is 5 minutes or more.
The invention according to claim 19 is the method according to any one of claims 1 to 16, wherein the time to reach the lowest cooling temperature is one hour or more.
The invention according to claim 20 is the method according to any one of claims 1 to 16, wherein the time required for temperature rise is 5 minutes or less.
The invention according to claim 21 is the method according to any one of claims 1 to 16, wherein the time required for temperature rise is 5 minutes or more.
The invention according to claim 22 is the method according to any one of claims 1 to 16, wherein the time required for the temperature rise is 1 hour or more.
The invention according to claim 23 is the method according to any one of claims 1 to 22, wherein the catalyst and the semiconductor are directly contacted with liquid nitrogen and cooled.
The invention of claim 24 is the method according to any one of claims 1 to 23, wherein after cooling, the catalyst or semiconductor is returned to room temperature by being left at room temperature.
The invention of claim 25 is a wet battery performance improving method and manufacturing method using the method of any one of claims 1-8, 12-24.
本発明は、触媒の活性を向上させる方法及び活性の向上した触媒の製造方法であって、いずれも、触媒を−３０℃以下に冷却し、冷却後昇温することを特徴とする方法であることを特徴とする。
触媒の冷却温度は、低ければそれだけ触媒活性の向上効果は高く、例えば、−３０℃以下であれば、目に見える向上効果が得られ始める。そして、冷却温度は例えば、−５０℃以下であることが望ましく、−８０℃以下であることが好ましく、冷却温度が−８０℃以下であれば、確実に向上効果が得られるので、実際には−８０℃以下での処理方法が望ましい。−８０℃以下の条件は地表上の自然条件としては存在しないので、なんらかの処理装置を使用することが必要である。さらに、冷却温度が液体窒素の温度（−１９６℃）以下であれば、より著しい向上効果が得られる。経済性と向上効果とのバランスを考慮すると液体窒素温度での冷却処理が好適である。
The present invention is a method for improving the activity of a catalyst and a method for producing a catalyst with improved activity, both of which are characterized in that the catalyst is cooled to -30 ° C or lower and the temperature is raised after cooling. It is characterized by that.
The lower the cooling temperature of the catalyst, the higher the catalyst activity improving effect. For example, when the catalyst cooling temperature is −30 ° C. or lower, a visible improving effect starts to be obtained. And, for example, the cooling temperature is desirably −50 ° C. or less, preferably −80 ° C. or less, and if the cooling temperature is −80 ° C. or less, an improvement effect is surely obtained. A treatment method at −80 ° C. or lower is desirable. Since a condition of −80 ° C. or lower does not exist as a natural condition on the surface of the earth, it is necessary to use some kind of processing apparatus. Furthermore, if the cooling temperature is equal to or lower than the temperature of liquid nitrogen (−196 ° C.), a more remarkable improvement effect can be obtained. Considering the balance between economic efficiency and improvement effect, the cooling treatment at the liquid nitrogen temperature is suitable.
冷却時間には、特に制限はなく、冷却温度や所望の向上効果を考慮して、適宜決定できるが、５分以上が通常であり、実用上は、３０分〜４８時間の範囲であることができる。ここで冷却時間とは最も低い冷却温度近傍に達してから昇温処理に入るまでの間の時間を指す。 The cooling time is not particularly limited and can be appropriately determined in consideration of the cooling temperature and the desired improvement effect, but it is usually 5 minutes or longer, and practically, it is in the range of 30 minutes to 48 hours. it can. Here, the cooling time refers to the time from the vicinity of the lowest cooling temperature to the start of the temperature raising process.
本発明において、最も低い冷却温度に達するまでの時間は重要であり、特に触媒の活性を高めるという観点からは最も低い冷却温度に達するまでの過程を緩和した方が良い場合がある。
たとえば、室温から冷却器に酸化物、たとえば酸化チタンを入れ、徐々に冷却する方が、液体窒素に直接酸化チタン粉を接触させるより、活性の向上の面で効果的である場合が多い。最も低い冷却温度に達するまでの時間は５分以上、場合により１時間を超えた方が良い場合がある。１時間を超えた場合、大きく特性が向上することが多い。
In the present invention, the time to reach the lowest cooling temperature is important. In particular, from the viewpoint of increasing the activity of the catalyst, it may be better to relax the process to reach the lowest cooling temperature.
For example, it is often more effective in terms of improving the activity to put an oxide, for example, titanium oxide, into a cooler from room temperature and gradually cool it, rather than bringing titanium oxide powder into direct contact with liquid nitrogen. The time to reach the lowest cooling temperature is preferably 5 minutes or more, and in some cases it may be better to exceed 1 hour. When it exceeds 1 hour, the characteristics are often greatly improved.
昇温に要する時間についても同様に実際に触媒の活性、を高めるという点からは５分以上、場合により１時間を超えた方が良い場合もある。この場合も１時間を超えた場合、大きく特性が向上することが多い。５時間以上、特に２４時間前後の時間をかけてゆっくり昇温することにより、特性が向上する場合もある。 Similarly, the time required for raising the temperature is preferably 5 minutes or more, and in some cases it may be better to exceed 1 hour in order to actually increase the activity of the catalyst. Also in this case, when the time exceeds one hour, the characteristics are often greatly improved. Characteristics may be improved by slowly raising the temperature over a period of 5 hours or more, particularly around 24 hours.
ただし、直接、液体窒素に接触させて冷却する方が触媒活性が向上する場合もある。たとえば同じ酸化チタンであっても、品種によってはゆっくり冷却した方が触媒活性、特に光触媒活性が向上するものもあれば、直接液体窒素に接触させた方が触媒活性、特に光触媒活性が向上するものもある。この理由については必ずしも明確ではないが、急激な冷却処理と、後の昇温処理により凝集した微結晶がほぐれる等の作用が複雑に関係しているものと予想できる。 However, there are cases where the catalytic activity is improved by cooling by direct contact with liquid nitrogen. For example, even if the same titanium oxide is used, depending on the varieties, there are those that are slowly cooled to improve catalytic activity, especially photocatalytic activity, and those that are directly contacted with liquid nitrogen improve catalytic activity, especially photocatalytic activity. There is also. Although the reason for this is not necessarily clear, it can be expected that an action such as a rapid cooling process and a breakup of microcrystals aggregated by a subsequent temperature increase process are complicatedly related.
冷却後の触媒を、常温に放置して触媒の温度を常温に戻す場合、冷却処理及び常温への戻しの処理は、容器内に密閉して行うことが、触媒への氷等の付着を防止すると言う観点から好ましい場合がある。 When the cooled catalyst is allowed to stand at room temperature and the temperature of the catalyst is returned to room temperature, the cooling process and the process of returning to room temperature should be performed in a sealed container to prevent adhesion of ice or the like to the catalyst. In some cases, this is preferable.
本発明の方法において、処理される触媒は、例えば、酸化物を含む物質であることができる。また、本発明の方法において、処理される触媒は、例えば、光触媒または通常の熱触媒であることもできる。 In the method of the present invention, the catalyst to be treated can be, for example, a substance containing an oxide. In the method of the present invention, the catalyst to be treated can be, for example, a photocatalyst or a normal thermal catalyst.
さらに、光触媒は、酸化物半導体（例えば、酸化チタン）である事ができる。光触媒は、公知の光触媒であればよく、光触媒としての機能を持つものであれば特に制限は無く、酸化亜鉛や他の酸化物半導体、あるいは酸窒化物半導体でもよいが、たとえば酸化チタンであれば、アナターゼ型、ルチル型、ブルッカイト型のものを適宜使用することができる。紫外活性をもつものだけでなく、青色に応答する可視応答型酸化チタンも使用することができる。本発明の処理を施して、活性向上に供することができる光触媒の例としては、例えば、再表01/010552、再表01/010553、特開2002-097019、特開2002-66333、特開2000-140636、特開2002-255554、特開2004-160327、特許3215698、特許3252136、WO 03/011763、WO 03/061828, WO03/080244、特開2004-160327等に記載のものを挙げることができるが、これらに限定される物ではない。 Furthermore, the photocatalyst can be an oxide semiconductor (eg, titanium oxide). The photocatalyst may be a known photocatalyst, and is not particularly limited as long as it has a function as a photocatalyst, and may be zinc oxide, other oxide semiconductors, or oxynitride semiconductors. Anatase, rutile, and brookite types can be used as appropriate. Not only those having ultraviolet activity, but also visible response type titanium oxide which responds to blue can be used. Examples of photocatalysts that can be subjected to the treatment of the present invention and can be used for activity improvement include, for example, Table 01/010552, Table 01/010553, JP 2002-097019, JP 2002-66333, JP 2000 -140636, JP2002-255554, JP2004-160327, JP3215698, JP3252136, WO03 / 011763, WO03 / 061828, WO03 / 080244, JP2004-160327, and the like. However, it is not limited to these.
特に、本発明の方法は、酸化物半導体とりわけ酸化チタンを冷却処理することを特徴とする。冷却する方法は特に制限は無いが、冷却処理後光触媒体表面に処理工程における残存物が存在しない方法がよい。この点配慮すれば冷却方法は公知のいかなる方法でもよく、液体ヘリウム、液体窒素による冷却方法が好適であるし、また、冷却温度に性能上の限界があるものの、食品冷凍に使用する機器等も使用できる。また、いわゆるクライオ装置の使用は有効である。 In particular, the method of the present invention is characterized in that an oxide semiconductor, particularly titanium oxide, is subjected to a cooling treatment. Although there is no restriction | limiting in particular in the method to cool, The method in which the residue in a process does not exist in the photocatalyst body surface after a cooling process is good. In consideration of this point, the cooling method may be any known method, and a cooling method using liquid helium or liquid nitrogen is suitable, and although there is a limit on the performance of the cooling temperature, equipment used for food freezing, etc. Can be used. Use of a so-called cryo device is effective.
本発明の性能向上方法において、なぜ光触媒活性が向上するかについてはかならずしも明瞭ではないが、酸化物半導体の結晶のなんらかの歪（ストレス）ないしは欠陥が冷却処理時および常温への昇温時にある程度解消、あるいは変化することにより、光吸収により励起されたホール（正孔）とキャリア（電子）の再結合を阻害する要因が減少したのではないかとも考えられる。本発明の性能向上方法により改質された光触媒体は冷却処理前と比して良好な光触媒活性を示し、有機ガスの分解作用他の機能を発揮する。本発明は、酸化チタンを用いた湿式太陽電池の性能向上手法、および製造法でもあるが、本発明の冷却処理、昇温処理を行った酸化チタンを使用した湿式太陽電池の効率が、本発明の冷却処理、昇温処理を行わない酸化チタンを使用した場合に比し高効率であることも、同様の理由に基づくことが考えられる。 In the performance improvement method of the present invention, it is not always clear why the photocatalytic activity is improved, but some distortion (stress) or defect of the crystal of the oxide semiconductor is eliminated to some extent at the time of cooling treatment and raising the temperature to room temperature, Alternatively, it is considered that the factor that inhibits the recombination of holes (holes) and carriers (electrons) excited by light absorption may have decreased due to the change. The photocatalyst modified by the method for improving performance of the present invention exhibits better photocatalytic activity than before the cooling treatment, and exhibits other functions such as the decomposition of organic gas. Although the present invention is a method for improving the performance of a wet solar cell using titanium oxide and a manufacturing method, the efficiency of the wet solar cell using titanium oxide subjected to the cooling treatment and the temperature raising treatment of the present invention is the present invention. It is conceivable that it is based on the same reason that it is more efficient than the case of using titanium oxide that is not subjected to the cooling treatment and the temperature raising treatment.
さらに酸化物を製造する方法として、水酸化物を加熱する方法が公知の方法としてあるが、水酸化物を冷却処理し、後に加熱することにより、結晶成長が抑えられる場合があることを本発明者は見出している。たとえばWO 03/011763の実施例2の洗浄5の条件で作成された水酸化チタン（アモルファスチタン）を原料として液体窒素で４時間冷却したものを試料として、４００℃で加熱した場合、液体窒素での冷却処理を行う前の原料を同様に４００℃で加熱したものに比し、XRDで解析した場合、アナターゼの結晶ピークが約５０％から６０％の強度（高さ）に減少する。このことは、結晶成長が水酸化物の冷却処理により結果として抑えられたことを意味する。結晶成長の制御により粒径の小さな酸化物を得ることも可能であり、結果として、活性の高い触媒、光触媒を得ることも期待できる。 Further, as a method for producing an oxide, a method of heating a hydroxide is a known method, but it is the present invention that crystal growth may be suppressed by cooling the hydroxide and heating it later. Have found headlines. For example, when titanium hydroxide (amorphous titanium) prepared under the conditions of cleaning 5 of Example 2 of WO 03/011763 is used as a raw material and cooled for 4 hours with liquid nitrogen, when heated at 400 ° C., the liquid nitrogen When the raw material before the cooling treatment is similarly heated at 400 ° C. and analyzed by XRD, the crystal peak of anatase is reduced from about 50% to 60% strength (height). This means that crystal growth was consequently suppressed by the cooling treatment of hydroxide. It is possible to obtain an oxide having a small particle diameter by controlling crystal growth, and as a result, it can be expected to obtain a highly active catalyst or photocatalyst.
本発明の性能向上方法は光触媒のみならず、金属酸化物を使用した触媒（熱触媒）、すなわち自動車の排ガス浄化用の三元触媒や、脱硫、脱硝触媒、各種合成用の触媒にも一定程度の有効性を示すものと期待される。当然、貴金属を担置した触媒にも一定の効果は期待できる。 The performance improvement method of the present invention is not limited to photocatalysts but also to catalysts using metal oxides (thermal catalysts), that is, three-way catalysts for exhaust gas purification of automobiles, desulfurization, denitration catalysts, and various synthesis catalysts. It is expected to show the effectiveness of. Of course, a certain effect can also be expected for a catalyst carrying a precious metal.
さらに本発明は、半導体の性能を向上させる方法及びであって、性能の向上した半導体の製造方法であって、いずれの方法も半導体を−３０℃以下に冷却することを特徴とする。 Furthermore, the present invention is a method for improving the performance of a semiconductor, and a method for manufacturing a semiconductor with improved performance, both of which are characterized in that the semiconductor is cooled to −30 ° C. or lower.
半導体の冷却温度は、低ければそれだけ半導体性能の向上効果は高く、例えば、−３０℃以下であれば、目に見える向上効果が得られ始める。そして、冷却温度は例えば、−５０℃以下であることが望ましく、−８０℃以下であることが好ましく、冷却温度が−８０℃以下であれば、確実に向上効果が得られる。さらに、冷却温度が液体窒素の温度（−１９６℃）以下であれば、著しい向上効果が得られる。経済性と向上効果とのバランスを考慮すると液体窒素での冷却処理が好適である。 The lower the semiconductor cooling temperature, the higher the semiconductor performance improvement effect. For example, when the semiconductor cooling temperature is −30 ° C. or lower, a visible improvement effect starts to be obtained. For example, the cooling temperature is desirably −50 ° C. or less, preferably −80 ° C. or less, and if the cooling temperature is −80 ° C. or less, the improvement effect is surely obtained. Furthermore, if the cooling temperature is equal to or lower than the temperature of liquid nitrogen (−196 ° C.), a significant improvement effect can be obtained. Considering the balance between economic efficiency and improvement effect, cooling treatment with liquid nitrogen is preferable.
冷却時間には、特に制限はなく、冷却温度や所望の向上効果を考慮して、適宜決定できるが、冷却時間は、５分以上が通常であり、実用上は、３０分〜４８時間の範囲であることができる。ここで冷却時間とは最冷却温度近傍に達してから昇温処理に入るまでの間の時間を指す。 The cooling time is not particularly limited and can be appropriately determined in consideration of the cooling temperature and a desired improvement effect. However, the cooling time is usually 5 minutes or more, and is practically in the range of 30 minutes to 48 hours. Can be. Here, the cooling time refers to the time from reaching the vicinity of the lowest cooling temperature until the temperature raising process is started.
本発明においては、最冷却温度に達するまでの時間は重要であり、特に半導体、（化合物半導体を含む）の性能を高めるという観点からは最も低い冷却温度に達するまでの過程を緩和した方が良い場合がある。
たとえば、室温から冷却器にシリコンウエハー、あるいはLEDを入れ、徐々に冷却する方が、活性の向上の面で効果的である場合が多い。最も低い冷却温度に達するまでの時間は５分以上が望ましく、基本的には１時間を超えた方が良い。１時間を超えた場合、大きく特性が向上することが多い。
In the present invention, the time to reach the lowest cooling temperature is important. In particular, from the viewpoint of enhancing the performance of semiconductors (including compound semiconductors), it is better to relax the process until the lowest cooling temperature is reached. There is a case.
For example, in many cases, it is more effective in terms of improving the activity to gradually cool a room by placing a silicon wafer or LED in a cooler. The time to reach the lowest cooling temperature is preferably 5 minutes or more, and basically it is better to exceed 1 hour. When it exceeds 1 hour, the characteristics are often greatly improved.
昇温に要する時間についても同様に半導体、（化合物半導体を含む）の性能を高めるという観点からは５分以上が望ましく、基本的には１時間を超えた方が良い。この場合も１時間を超えた場合、大きく特性が向上することが多い。５時間以上、特に２４時間前後の時間をかけてゆっくり昇温することにより、特性が向上する場合もある。 Similarly, the time required for raising the temperature is preferably 5 minutes or more from the viewpoint of enhancing the performance of the semiconductor (including the compound semiconductor), and basically it is better to exceed 1 hour. Also in this case, when the time exceeds one hour, the characteristics are often greatly improved. Characteristics may be improved by slowly raising the temperature over a period of 5 hours or more, particularly around 24 hours.
冷却後の半導体は、クライオ装置等を利用して徐々に昇温することが普通であるが、場合によっては常温に放置して半導体の温度を常温に戻す場合もある。冷却処理及び常温への戻しの処理は、容器内に密閉して行うことが、半導体への氷等の付着を防止すると言う観点から好ましい場合がある。 Normally, the semiconductor after cooling is gradually heated using a cryo device or the like, but in some cases, the temperature of the semiconductor may be returned to room temperature by leaving it at room temperature. The cooling process and the process of returning to room temperature may be preferably performed in a sealed manner in a container from the viewpoint of preventing adhesion of ice or the like to the semiconductor.
本発明において半導体は、特に制限はないが、例えば、シリコン太陽電池であることができ、シリコン太陽電池は、例えば、単結晶、微結晶、多結晶またはアモルファス型であることができる。シリコン太陽電池を本発明の方法で処理すると、電流特性（光−電気変換特性）が向上する。
また、本発明において半導体は、GaAs等の化合物半導体であることもできる。
化合物半導体は発光LEDであることもできる。
In the present invention, the semiconductor is not particularly limited, but can be, for example, a silicon solar cell, and the silicon solar cell can be, for example, a single crystal, a microcrystal, a polycrystalline, or an amorphous type. When a silicon solar cell is processed by the method of the present invention, current characteristics (photo-electric conversion characteristics) are improved.
In the present invention, the semiconductor can also be a compound semiconductor such as GaAs.
The compound semiconductor can also be a light emitting LED.
本発明において湿式太陽電池はいわゆる色素と酸化チタン、ITO等の透明性導電極、電解質液等で構成されるグレッチエルセル型であることができるが、本発明の冷却処理他を施す酸化チタンは熱加水分解でできたアナターゼ型やルチル型であることができるし、硫酸チタン、硫酸チタニルや四塩化チタン、三塩化チタンをアンモニアや水酸化ナトリウム、水酸化リチウム、水酸化カリウム等で共沈させた水酸化物を空気中あるいは水溶液中で加熱してルチル型、あるいはアナターゼ型、場合によりブルッカイト型に結晶化したものが適宜使用可能である。その他酸化チタンの製法は公知のいかなる製法でも良いが、本発明の冷却処理他を行ったことによる性能向上の程度は結晶性が比較的低いもの、すなわち、(XRDでブロードなピークを示すタイプの比較的BET被表面積の大きな酸化チタン)、たとえば、溶液中で熱加水分解法されることにより製造された、石原産業製のST-01の様なタイプの酸化チタンに顕著である傾向がある。
このタイプの酸化チタンはアモルファス相と微結晶相との混晶である場合が多い。なお、酸化チタン粉が溶液に分散している状態であっても基本的な問題は無く、本発明の技術を使用することも適宜可能である。
In the present invention, the wet solar cell can be a Gretsch-Elsell type composed of a so-called pigment, titanium oxide, a transparent conductive electrode such as ITO, an electrolyte solution, etc. It can be anatase type or rutile type made by thermal hydrolysis, and titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride are coprecipitated with ammonia, sodium hydroxide, lithium hydroxide, potassium hydroxide, etc. Further, it is possible to appropriately use a hydroxide obtained by heating the hydroxide in the air or in an aqueous solution and crystallizing it into a rutile type, anatase type or, in some cases, a brookite type. In addition, any known production method of titanium oxide may be used, but the degree of performance improvement by performing the cooling treatment of the present invention is relatively low in crystallinity, i.e. (of the type showing a broad peak in XRD). Titanium oxide having a relatively large BET surface area), for example, a type of titanium oxide such as ST-01 manufactured by Ishihara Sangyo, manufactured by thermal hydrolysis in a solution tends to be prominent.
This type of titanium oxide is often a mixed crystal of an amorphous phase and a microcrystalline phase. Even if the titanium oxide powder is dispersed in the solution, there is no basic problem, and the technique of the present invention can be used as appropriate.
なお、本発明の応用として、磁性体を冷却することにより、インダクタンスが大となる傾向も本発明者は見出している。たとえば電力用のトランスに使用されるアモルファスの鉄コアを-85℃で４時間以上冷却処理した場合、インダクタンスが処理前に比し１割程度向上することが確認されている。 As an application of the present invention, the present inventors have also found that the inductance tends to increase by cooling the magnetic material. For example, it has been confirmed that when an amorphous iron core used in a power transformer is subjected to a cooling treatment at -85 ° C. for 4 hours or more, the inductance is improved by about 10% as compared with that before the treatment.
以下に本発明を実施例及び比較例によって具体的に説明するが、本発明はかかる事例に限定されるものではない。
実施例１
試料の調製方法
WO 03/011763の実施例2の洗浄5の条件(400℃で1時間焼成)に従って作成した可視光に応答する光触媒2.0gを冷凍機を使用して２0℃−から−80℃の雰囲気にするのに5時間かかる条件で温度を下げて、−80℃の雰囲気は４時間維持後5時間かけて２0℃に戻して試料１を得た。また、同様の光触媒2.0gを２0℃から液体窒素温度近傍の温度雰囲気にするのに12時間かかる条件で温度を下げて、液体窒素温度近傍の雰囲気は４時間維持後、12時間かけて２0℃に戻して試料２を得た。
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to such examples.
Example 1
Sample preparation method
Using a refrigerator, 2.0 g of a photocatalyst responding to visible light prepared according to the conditions of cleaning 5 in Example 2 of WO 03/011763 (calcined at 400 ° C. for 1 hour) is brought to an atmosphere of 20 ° C. to −80 ° C. Then, the temperature was lowered under conditions that took 5 hours, and the atmosphere at −80 ° C. was maintained for 4 hours and then returned to 20 ° C. over 5 hours to obtain Sample 1. In addition, the temperature of the same photocatalyst 2.0 g was lowered from 20 ° C. under the condition that it took 12 hours to change to a temperature atmosphere near liquid nitrogen temperature, and the atmosphere near liquid nitrogen temperature was maintained for 4 hours and then 20 ° C. over 12 hours. Sample 2 was obtained by returning to step (b).
光触媒評価方法：
試料を0.2ｇを採取後、６cm×６cmのガラス板に蒸留水を加えながら均一に塗布した。その後、試料を乾燥させ550ｍLのガラス製反応容器内に設置した。反応容器を5Torrまで脱気させ，高純度空気(日本酸素製，CO2、0.5ppm以下)で760Torrまで戻した。反応容器内にアセトン約550ppmになるように液体の状態で注入し、気化させた。吸着平衡後に青色LED( 日亜化学製、NSPB500S、中心波長470nmを23個配列）を24時間照射させた。アセトン濃度はガスクロマトグラフ（FID）で、CO2濃度はガスクロマトグラフ(TCD)で測定を行なった。未処理の光触媒(未処理品)、試料1及び2の結果を以下の表１及び図１に示す。
Photocatalyst evaluation method:
After collecting 0.2 g of the sample, it was uniformly applied to a 6 cm × 6 cm glass plate while adding distilled water. The sample was then dried and placed in a 550 mL glass reaction vessel. The reaction vessel was degassed to 5 Torr and returned to 760 Torr with high purity air (Nippon Oxygen, CO 2 , 0.5 ppm or less). Into the reaction vessel, acetone was injected in a liquid state to be about 550 ppm and vaporized. After the adsorption equilibrium, a blue LED (manufactured by Nichia Chemical Co., Ltd., NSPB500S, 23 arrays with a central wavelength of 470 nm) was irradiated for 24 hours. The acetone concentration was measured with a gas chromatograph (FID), and the CO 2 concentration was measured with a gas chromatograph (TCD). The results of untreated photocatalyst (untreated product) and Samples 1 and 2 are shown in Table 1 and FIG.
実施例２
試料の調製方法：
市販の光触媒であるST-01（石原産業製）2.0gを液体窒素中にいきなり投入し、4時間放置し、放置後室温に戻して自然に昇温させて試料３を得た。
Example 2
Sample preparation method:
ST-01 (manufactured by Ishihara Sangyo Co., Ltd.), a commercially available photocatalyst, was suddenly charged into liquid nitrogen, allowed to stand for 4 hours, allowed to return to room temperature, and naturally warmed to obtain sample 3.
光触媒評価方法：
試料0.2ｇを採取後、６cm×６cmのガラス板に蒸留水を加えながら均一に塗布した。その後、試料を乾燥させ550ｍLのガラス製反応容器内に設置した。反応容器を5Torrまで脱気させ、高純度空気(日本酸素製、CO2、0.5ppm以下)で760Torrまで戻した。反応容器内にアセトン約550ppmになるように液体の状態で注入し、気化させた。吸着平衡後にブラックライト( SANKYOU DENKI製、FL10BLB、10W、1本、照射距離10 cm）を照射させた。CO2濃度はガスクロマトグラフ(TCD)で測定を行なった。未処理のST-01(未処理品)及び試料3の結果を表2に示す。
Photocatalyst evaluation method:
After collecting 0.2 g of a sample, it was uniformly applied to a 6 cm × 6 cm glass plate while adding distilled water. The sample was then dried and placed in a 550 mL glass reaction vessel. The reaction vessel was degassed to 5 Torr, and returned to 760 Torr with high purity air (manufactured by Nippon Oxygen, CO 2 , 0.5 ppm or less). Into the reaction vessel, acetone was injected in a liquid state to be about 550 ppm and vaporized. After the adsorption equilibrium, a black light (manufactured by SANKYOU DENKI, FL10BLB, 10W, 1 piece, irradiation distance 10 cm) was irradiated. The CO 2 concentration was measured with a gas chromatograph (TCD). Table 2 shows the results of untreated ST-01 (untreated product) and Sample 3.
実施例１．２ともに本発明の冷却処理他を行うことにより、この処理を行わない比較例の試料より光触媒活性が向上していることがわかる。
実施例３
シリコン太陽電池(形状10cm φ 円形)型番T500-2V(RQ)（定格電流500mA 定格電圧2V）を試験用の太陽電池セルとした。
（測定１）
この試験用セルに蛍光灯を照射し、発生した電流及び電圧の測定を行った。測定は１秒に１回行い480秒（480回）測定し、その平均値を演算し求めた。
It can be seen that by performing the cooling treatment of the present invention in Example 1.2, the photocatalytic activity is improved over the sample of the comparative example in which this treatment is not performed.
Example 3
A silicon solar cell (10 cm diameter circular), model number T500-2V (RQ) (rated current 500 mA, rated voltage 2 V) was used as a test solar cell.
(Measurement 1)
The test cell was irradiated with a fluorescent lamp, and the generated current and voltage were measured. The measurement was performed once per second, measured for 480 seconds (480 times), and the average value was calculated.
（測定２）
上記試験用セルを冷却器に入れた。冷却器では20℃から５時間かけて−85℃まで雰囲気温度を下げた。この−85℃の雰囲気で４時間冷却し、その後５時間かけて20℃に戻した。
その後、測定１と同一条件での試験を行った。
(Measurement 2)
The test cell was placed in a cooler. In the cooler, the ambient temperature was lowered from 20 ° C. to −85 ° C. over 5 hours. It cooled in this atmosphere of -85 degreeC for 4 hours, and returned to 20 degreeC over 5 hours after that.
Thereafter, a test was performed under the same conditions as in Measurement 1.
尚、上記測定で用いた蛍光灯は，無電極「パルックボール」電球型蛍光灯６０ワット形（消費電力12W） 型番PFAED/12 松下電器産業株式会社 照明社製である。また、照度の測定には、照度計（3423ルクスハイテスタ 日置電機株式会社製）を使用した。また、電圧及び電流の測定には、テスター（デジタルマルチメーター Metex Model:ME22T（METEX CORPORATION製））を使用した。 The fluorescent lamp used in the above measurement is an electrodeless “Palook ball” bulb type fluorescent lamp 60 watts (power consumption 12 W), model number PFAED / 12, manufactured by Matsushita Electric Industrial Co., Ltd. An illuminance meter (3423 Lux Hitester, Hioki Electric Co., Ltd.) was used for illuminance measurement. In addition, a tester (digital multimeter Metex Model: ME22T (manufactured by METEX CORPORATION)) was used to measure voltage and current.
実験用太陽電池セルの電極+-に上記のテスターを接続し、蛍光灯を照射した。測定1および測定２双方で実験用セルの表面での照度計が1.2万ルクスを示すように蛍光灯の位置を設定した。測定１では電流値（短絡電流）は18.77mAのであったのに対し、測定２では20.01mAであり、発生電流量は約6％、増加した。 The above tester was connected to the electrode +-of the solar cell for experiment and irradiated with a fluorescent lamp. In both Measurement 1 and Measurement 2, the position of the fluorescent lamp was set so that the illuminometer on the surface of the experimental cell showed 12,000 lux. In measurement 1, the current value (short-circuit current) was 18.77 mA, whereas in measurement 2, it was 20.01 mA, and the amount of generated current increased by about 6%.
次に実験用電池セルの電極+−に負荷抵抗を接続し、電圧を測定した。結果を以下の表3に示す。 Next, a load resistance was connected to the electrode + − of the experimental battery cell, and the voltage was measured. The results are shown in Table 3 below.
上記表3に示す結果から、測定２では測定１に比し発生電圧がいずれも大きくなっていることがわかる。即ち、本発明の方法により−85℃に本発明の処理を行うことによりシリコン太陽電池の発電特性が向上したことがわかる。
実施例４
次に湿式電池に使用した場合の例を記述する。以下の実施例において作製した電池は、その電極面積が１×１ｃｍである。また、電池を作動させる光源として、５００ｗのキセノンランプを用い、そのランプからの４２０ｎｍ以下の波長の光はフィルターでカットした。また、作製した電池について、その短絡電流及び開放電圧の測定に無抵抗電流計を備えたポテンシオスタットを用いた。また、使用した酸化物半導体粉末において、ＴｉＯ2としてはWO 03/011763の実施例2の洗浄5の条件(400℃で1時間焼成)に従って作成した可視光に応答する光触媒を原料とし、20℃から液体窒素温度雰囲気に達するのに８時間かけ、また、液体窒素温度雰囲気で８時間冷却した後に８時間かけて20℃まで昇温したものを用い、また、有機色素としては、Ｒｏ（ローズベンガル）を用いた。比較例としてはWO 03/011763の実施例2の洗浄5の条件(400℃で1時間焼成)に従って作成した可視光に応答する光触媒それ自体を本発明の冷却処理他をせずに用いた。
From the results shown in Table 3 above, it can be seen that in measurement 2, the generated voltage is higher than that in measurement 1. That is, it can be seen that the power generation characteristics of the silicon solar cell were improved by performing the treatment of the present invention at −85 ° C. by the method of the present invention.
Example 4
Next, an example of use in a wet battery will be described. The batteries produced in the following examples have an electrode area of 1 × 1 cm. A 500 w xenon lamp was used as a light source for operating the battery, and light having a wavelength of 420 nm or less from the lamp was cut by a filter. Moreover, about the produced battery, the potentiostat provided with the non-resistance ammeter was used for the measurement of the short circuit current and open circuit voltage. In addition, in the oxide semiconductor powder used, as a raw material, a photocatalyst responding to visible light prepared according to the conditions of cleaning 5 in Example 2 of WO 03/011763 (calcined at 400 ° C. for 1 hour) as TiO 2 , 20 ° C. It takes 8 hours to reach the liquid nitrogen temperature atmosphere, and after cooling for 8 hours in the liquid nitrogen temperature atmosphere, the temperature is raised to 20 ° C. over 8 hours. The organic dye is Ro (Rose Bengal). ) Was used. As a comparative example, the photocatalyst itself responding to visible light prepared according to the conditions of cleaning 5 of Example 2 of WO 03/011763 (calcined at 400 ° C. for 1 hour) was used without the cooling treatment of the present invention.
湿式電池は以下のようにして作製した。前記ＴｉＯ2（WO 03/011763の実施例2の洗浄5の条件(400℃で1時間焼成)に従って作成した可視光に応答する光触媒を上記の方法、すなわち液体窒素温度で本発明の冷却処理他をしたもの）を非イオン性界面活性剤を含む水とアセチルアセトンとの混合液（容量混合比＝２０／１）中に濃度約１ｗｔ％で分散させてスラリー液を調製した。次に、このスラリー液を厚さ１ｍｍの導電性ガラス基板（Ｆ−ＳｎＯ2、１０Ω／ｓｑ）上に塗布し、乾燥し、得られた乾燥物を５００℃で１時間、空気中で焼成し、基板上に厚さ７μｍの焼成物膜を形成した。次に、この焼成物膜を基板とともに、有機色素溶液中に浸漬し、８０℃で、還液を行いながら、色素吸着処理を行った後、室温で乾燥した。この場合、有機色素溶液は、Ｆ１を除き、有機色素を１００ｍｇ／１００ｍｌの濃度でエタノール中に溶解して調製した。また、Ｆ１溶液はＦ１を１００ｍｇ／１００ｍｌ濃度でジメチルホルムアミド中に、溶解して調製した。 The wet battery was produced as follows. The photocatalyst responding to visible light prepared according to the above-described TiO 2 (cleaning condition 5 in Example 2 of WO 03/011763 (calcined at 400 ° C. for 1 hour)) is the above-described method, that is, the cooling treatment of the present invention at liquid nitrogen temperature Was dispersed in a mixed liquid of water containing nonionic surfactant and acetylacetone (volume mixing ratio = 20/1) at a concentration of about 1 wt% to prepare a slurry liquid. Next, this slurry solution is applied onto a 1 mm thick conductive glass substrate (F-SnO 2 , 10Ω / sq) and dried, and the obtained dried product is baked in air at 500 ° C. for 1 hour. A fired product film having a thickness of 7 μm was formed on the substrate. Next, this fired product film was immersed in an organic dye solution together with the substrate, subjected to dye adsorption treatment while returning the solution at 80 ° C., and then dried at room temperature. In this case, the organic dye solution was prepared by dissolving F1 in ethanol at a concentration of 100 mg / 100 ml, except for F1. The F1 solution was prepared by dissolving F1 at a concentration of 100 mg / 100 ml in dimethylformamide.
前記のようにして得た酸化物半導体電極とその対極とを電解質液に接触させて太陽電池を構成した。この場合、対極としては、白金を２０ｎｍ厚さで蒸着した導電性ガラスを用いた。両電極間の距離は１ｍｍとした。電解質液としては、テトラプロピルアンモニウムヨーダイド（０．４６Ｍ）とヨウ素（０．６Ｍ）を含むエチレンカーボネートとアセトニトリルとの混合液（容量混合比＝８０／２０）を用いた。 The oxide semiconductor electrode obtained as described above and its counter electrode were brought into contact with the electrolyte solution to form a solar cell. In this case, as the counter electrode, conductive glass in which platinum was deposited with a thickness of 20 nm was used. The distance between both electrodes was 1 mm. As the electrolyte solution, a mixed solution (volume mixing ratio = 80/20) of ethylene carbonate and acetonitrile containing tetrapropylammonium iodide (0.46M) and iodine (0.6M) was used.
比較例はＴｉＯ2としてWO 03/011763の実施例2の洗浄5の条件(400℃で1時間焼成)に従って作成した可視光に応答する光触媒それ自体を本発明の冷却処理他をせずに用いた以外はすべて実施例と同様の条件、手法で作成した。
実施例及び比較例の湿式電池ついて測定した、短絡電流及び開放電圧を表４に示す。
The comparative example uses TiO 2 as a photocatalyst itself that responds to visible light, prepared according to the conditions of cleaning 5 of Example 2 of WO 03/011763 (calcined at 400 ° C. for 1 hour) without using the cooling treatment of the present invention. Except for the above, all were prepared under the same conditions and methods as in the examples.
Table 4 shows the short-circuit current and the open-circuit voltage measured for the wet batteries of Examples and Comparative Examples.
上記表４に示す結果から、実施例では比較例に比し短絡電流及び解放電圧双方とも大きくなっていることがわかる。即ち、液体窒素で本発明の冷却処理等をしたＴｉＯ2を使用することにより湿式電池の発電特性が向上したことがわかる。
実施例５
日亜化学工業製 白色チップLED 型番 NSCW100を前後左右１cm間隔で縦１６個、横１６個、計２５６個を基板上にマトリクス状に配置し、実験用のLED基板とした。LEDの電気的な接続方法としては、図１に示すように、LED６４個毎に並列に電気的に接続したものを４ユニット作成し、それら４ユニットを直列に接続した。
From the results shown in Table 4, it can be seen that both the short-circuit current and the release voltage are higher in the example than in the comparative example. That is, it can be seen that the power generation characteristics of the wet cell are improved by using TiO 2 that has been subjected to the cooling treatment of the present invention with liquid nitrogen.
Example 5
White chip LED manufactured by Nichia Industry Co., Ltd. Model No. NSCW100 was arranged in matrix form on the substrate, with 16 vertical and 16 horizontal at 1 cm intervals in the front and rear, left and right, and used as an experimental LED substrate. As for the electrical connection method of the LEDs, as shown in FIG. 1, four units were prepared in which 64 LEDs were electrically connected in parallel, and these four units were connected in series.
このLED基板を、発光部を上にむけ、試験台の上に設置、固定した。そしてLED基板全体を 21cm×21cm, 高さ20cmの光を通さない素材の箱でおおった。
この箱の上部中央に照度計（日置製3423ルクスハイテスター）の受光部を設置した。
LED基板に電源（定電流制御、24V,1.5A）を接続し、発光ダイオードを発光させて照度を測定した。
電流値は50mAから550mAまで変化させ、その照度を測定した。（０アジャストは測定毎に行った）−これを測定１とする。その時の電圧値は１１．１８Ｖから１２．６Ｖであった。
This LED substrate was placed and fixed on a test bench with the light emitting part facing up. The entire LED board was covered with a 21cm x 21cm, 20cm high light-proof material box.
The light receiving part of the illuminometer (Hioki 3423 Lux High Tester) was installed in the upper center of this box.
A power supply (constant current control, 24V, 1.5A) was connected to the LED substrate, and the illuminance was measured by causing the light emitting diode to emit light.
The illuminance was measured by changing the current value from 50 mA to 550 mA. (0 adjustment was made for each measurement) —This is measurement 1. The voltage value at that time was 11.18V to 12.6V.
LED基板を冷却器に入れた後、20℃から５時間かけて−85℃まで雰囲気温度を下げた。この−85℃の雰囲気で４時間冷却し、その後５時間かけて20℃に戻した。
これを測定１と同様の手法を用い照度を測定した。これを測定２とする。結果を表１及び図２に示す。
After putting the LED substrate in the cooler, the ambient temperature was lowered from 20 ° C. to −85 ° C. over 5 hours. It cooled in this atmosphere of -85 degreeC for 4 hours, and returned to 20 degreeC over 5 hours after that.
The illuminance was measured using the same method as in Measurement 1. This is measured 2. The results are shown in Table 1 and FIG.
上記表５に示す結果から、実施例では比較例に比し同一電流での照度が増加していることがわかる。
From the results shown in Table 5, it can be seen that in the example, the illuminance at the same current is increased as compared with the comparative example.
Claims (25)
The performance improvement method and manufacturing method of a wet battery using the method in any one of Claims 1-8 and 12-24.
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| JP2004206701A Pending JP2006026487A (en) | 2004-07-14 | 2004-07-14 | Method of improving activity of catalyst and performance of semiconductor and method of manufacturing catalyst having improved activity, semiconductor having improved performance and wet solar cell |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101262325B1 (en) * | 2011-05-30 | 2013-05-09 | 연세대학교 산학협력단 | A method of making oxide thin film and a method of making thin film transistor |
| KR101528774B1 (en) * | 2013-12-02 | 2015-06-29 | 서울시립대학교 산학협력단 | Producing method of electrodes |
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2004
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101262325B1 (en) * | 2011-05-30 | 2013-05-09 | 연세대학교 산학협력단 | A method of making oxide thin film and a method of making thin film transistor |
| KR101528774B1 (en) * | 2013-12-02 | 2015-06-29 | 서울시립대학교 산학협력단 | Producing method of electrodes |
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